Process for the preparation of 2,2′-bis-indenyl biphenyl ligands and their metallocene complexes

ABSTRACT

The invention relates to a novel process for the preparation of 2,2′-bis indenyl biphenyl ligands of following formula (3): The invention also relates to metallocene complexes prepared using the novel process for the preparation of 2,2-bis indenyl biphenyl ligands. The invention also relates to novel intermediates used in the process for the preparation of 2,2′-bis indenyl biphenyl ligands.

This application is a national stage application of PCT/EP2014/067665filed Aug. 19, 2014, which claims priority to European ApplicationsEP13181090.5 filed Aug. 20, 2013, EP13181087.1 filed Aug. 20, 2013, andEP13181089.7 filed Aug. 20, 2013, which are hereby incorporated byreference in their entirety.

The present invention relates to a process for the preparation of2,2′-bis(2-indenyl)biphenyl ligands and their metallocene complexes. Theinvention also relates to novel intermediates in said process and to theprocess of the preparation of said intermediates.

Metallocene complexes with 2,2′-bis(2-indenyl)biphenyls ligands haveproven to be highly active in the polymerization of α-olefins, such asethylene after activation with aluminoxane cocatalysts. However, theknown syntheses of the ligands used in the synthesis of thesemetallocene complexes are tedious.

For instance, U.S. Pat. No. 6,342,622B1 describes a process for thepreparation of indenyl ligands, which are prepared using diboronic acid,which is prepared via the di-lithio complex of biphenyl. This di-lithiocomplex is highly pyrophoric and it is difficult to produce at a largescale. Further, the yields of the preparation of this di-lithio produceare not consistent and undesired byproducts, such as mono isomer areformed. In addition, the purification of the di-lithio product isdifficult and risky. Since pure di-lithio is required for diboronic acidpreparation, multiple washings of hexane are needed, which leads to alot of undesired organic waste, which is undesired from an environmentalpoint of view.

Ijpeij, E et al. describes in the Journal of Organic Chemistry, 2002,Vol. 67, pages 169-176, a process for bis Suzuki coupling. This processhowever again relies on a preparation via a di-lithio complex ofbiphenyl, which is highly pyrophoric and makes the up scaling of theprocess extremely difficult. In addition, the process uses a homogeneouscatalyst, such as Pd(PPh₃)₄, so that catalyst recovery can be difficult.Moreover, the bis-Grignard reaction described in this Journal of OrganicChemistry, 2002, Vol. 67, pages 169-176 and in Organometallics, 1993,Vol. 12, page 4391 requires very high dilution of the solvent (1:70) andis therefore also difficult to scale-up.

WO2013/091837A1 discloses a process comprising the step of reacting a2-indenylpinacolyl borane compound with a bromosubstituted compound inthe presence of a Pd catalyst and a base to form the correspondingbridged bis(indenyl) ligand. However, this process involves the use ofthe hazardous butyl lithium and requires a lot of energy. Also, theprocess is difficult to scale-up.

WO2013/091836A1 discloses a process comprising the step of (a) reactinga 2-indenylboranic acid (ester) with a bromosubstituted compound in thepresence of the Pd catalyst bis(triphenylphosphin)palladium dichloride(PPh₃)₂PdCl₂) and a base to form the corresponding bridged bis(indenyl)ligand. However, this process involves the use of the hazardous butyllithium and requires a lot of energy. Also, the process is difficult toscale-up.

It is the object of the invention to provide an improved process for thepreparation of 2,2′-bis(2-indenyl)biphenyls ligands.

This object is achieved by a process comprising the step of

reacting a compound of formula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryl orwherein R⁷ and R⁸ may form a ring together with the oxygen atoms towhich they are boundand wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H with a compound offormula (2)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² m are as definedherein and wherein X⁵ stands for a halogen in a solvent in the presenceof a Pd catalyst and a baseto form the corresponding compound of formula (3)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² m are as definedherein.

The process of the invention is easily upscaleable, gives consistentyields and is easy to work-up. Additionally, less by-products are formedand the process is less hazardous.

R¹, R², R³, R⁴, R⁵ and R⁶

R¹, R², R³, R⁴, R⁵ and R⁶ may each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B containinggroup or a P-containing group, preferably for H, a hydrocarbon radicalhaving 1-20 C-atoms or a halide. Examples of hydrocarbon radicalsincludes alkyl groups, for example methyl, ethyl, propyl, for examplei-propyl or n-propyl; butyl, for example i-butyl or n-butyl; hexyl anddecyl; aryl groups, for example phenyl, mesityl, tolyl and cumenyl;aralkyl groups for example benzyl, pentamethylbenzyl, xylyl, styryl andtrityl and alkaryl groups. The hydrocarbon radical preferably has from1-6 C-atoms and is most preferably methyl. Examples of halides includechloride, bromide and fluoride. Examples of alkoxy groups having 1-6C-atoms include but are not limited to methoxy, ethoxy and phenoxy.Examples of alkylsulphides include methylsulphide, phenylsulphide andn-butylsulphide. Examples of amines include dimethylamine, n-butylamine.Examples of Si or B containing groups include trimethylsilicium (Me₃Si)and diethylboron (Et₂B). Examples of P-containing groups includedimethylphosphor (Me₂P) and diphenylphosphor (Ph₂P).

Preferably, R⁵ and/or R⁶ stand for H. More preferably, R¹ and/or R²and/or R³ and/or R⁴ and/or R⁵ and/or R⁶ stand for H. Most preferably R¹,R², R³, R⁴, R⁵ and R⁶ all stand for H.

R⁷ and R⁸

R⁷ and R⁸ each independently stand for H, or an alkyl, for example acyclic or acylic alkyl, preferably a linear alkyl, such as i-propyland/or for example an alkyl having 1 to 6 carbon atoms or aryl, forexample phenyl or wherein R⁷ and R⁸ may form a ring together with theoxygen atoms to which they are bound, or for example R⁷ and R⁸ may forma pinacolyl ring or diamino ring together with the oxygen atoms to whichthey are bound. Preferably R⁷ and R⁸ stand for H or R⁷ and R⁸ form apinacolyl ring together with the oxygen atoms to which they are bound.

R⁹, R¹⁰, R¹¹ and R¹²

R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

X⁵

X⁵ stands for halogen, preferably Cl, Br or F, more preferably for Br.

The process to form the compound of formula (3) as described above mayin principle be performed in any solvent known to be suitable for Suzukicouplings, such as alcohols, for example methanol or ethanol; aromaticsolvents, for example benzene, toluene or xylene; ethers, for exampletetrahydrofuran, dioxane or dimethoxyethane; amides, for exampledimethylformamide and water that is preferably substantially free ofoxygen. Preferably organic solvents are used, more preferably aromaticsolvents, for example toluene. Mixtures of solvents, such as thesolvents mentioned herein may also be used, for example a mixture ofwater that is preferably substantially free of oxygen and an aromaticsolvent or a mixture of water with an alcohol such as ethanol.

The Pd catalysts that can be used in the preparation of the compound offormula (3) are in principle all Pd catalysts known to be suitable forSuzuki couplings. Preferably, a Pd(0) catalyst or a catalyst whereinPd(0) is generated in situ by reduction of (more stable) Pd(II)compounds is used. Examples of Pd catalysts includetetrakis(triphenylphosphin)palladium ((Ph₃P)₄Pd), palladium (II) acetate(Pd(O₂CCH₃)₂ or Pd(Oac)₂), tris(dibenzylideneacetone)dipalladium(PD(dba)₂), bis(triphenylphosphin)palladium dichloride (PPh₃)₂PdCl₂),1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II)(PdCl₂(dppf)), [1,2-bis(diphenylphosphino)ethane]dichloropalladium(II),(PdCl₂(dppe)), bis(tricyclohexyl phosphine)palladium(0),bis(triethylphosphine)palladium(II) chloride,bis(tri-t-butylphosphine)palladium(0),bis[1,2-bis(diphenylphosphino)ethane] palladium(0),bis[tri(o-tolyl)phosphine]palladium(II) chloride,trans-benzyl(chloro)bis(triphenylphosphine)palladium(II).

Preferably as Pd catalyst, tetrakis(triphenylphosphin)palladium(Pd(PPh₃)₄) or Pd on carbon (Pd/C) is used. Pd/C is thereby aheterogeneous catalysts and therefore very easy to recover and reuse.

The base that can be used in the preparation of the compound of formula(3) can in principle be any base, for example an inorganic or an organicbase. Preferably an organic base is used in the preparation of thebridged bis-indenyl) ligand of formula (3), such as for example aquaternary ammonium salt, for example tetra n-butylammoniumacetate ortetra-butyl ammonium hydroxide or a tertiary amine, for exampletriethylamine (Et₃N). Other examples of suitable bases include but arenot limited to sodium carbonate, sodium acetate, sodium tert-butoxide,potassium carbonate, potassium iodide, sodium iodide, potassium acetate,cesium carbonate, cesium fluoride, lithium hydroxide, sodium hydroxide,sodium ethoxide, potassium fluoride and potassium phosphate. Preferably,the base used in the reaction of the compound of formula (1) with thecompound of formula (2) is tetra-butyl ammonium hydroxide.

In principle, the reaction conditions for the process to form thecompound of formula (3) are not critical and the temperatures, pressuresand reaction time known to be suitable for Suzuki couplings, may be usedby the person skilled in the art and optimal conditions can be foundusing routine experimentation. For example, the temperature may be from60 to 120° C., as at temperatures below 60° C., the reaction hardlyproceeds and at temperatures of above 120° C., tarring may occur.Preferably, the temperature is chosen to be at least 60, preferably atleast 75 and/or at most 100, preferably at most 85° C. The pressureunder which the process is performed is preferably atmospheric pressure(1 bar). The reaction time may for example be in the range from 36 to 48hours.

The compound of formula (1) and (2) are preferably reacted in a molarratio of 1:1 to 1:4, preferably in a molar ratio of about 1:1.2.

In another embodiment, the invention also relates to the novel compoundof formula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing group andwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryl orwherein R⁷ and R⁸ may form a ring together with the oxygen atoms towhich they are bound and wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

The compound of formula (1), wherein R⁷ and R⁸ each independently standfor H, or an alkyl or aryl may be prepared using the process of theinvention, further comprising the step of preparing the compound offormula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryland wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H.is prepared by a process comprising the steps of protecting a compoundof formula (7)

wherein X³ stands for a halogenwherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H,and wherein R¹⁵ and R¹⁶ each independently stand for H, alkyl or aryl,with PG-LG, wherein PG stands for a protecting group and wherein LGstands for a leaving group to form the corresponding compound of formula(6)

wherein X³, R⁹, R¹⁰, R¹¹ and R¹² are as defined herein and wherein PGstands for the protecting groupreacting the compound of formula (6) with a compound of formula (5)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing group and wherein R¹³ and R¹⁴ each independentlystand for H, alkyl or aryl,in a solvent in the presence of a Pd catalyst and a base to form thecorresponding compound of formula (4)

wherein R¹, R², R³, R⁴, R⁵ and R⁶, R⁹, R¹⁰, R¹¹ and R¹² and PG are asdefined hereinand deprotecting the compound of formula (4) by reaction of the compoundof formula (4) with an acid to form the corresponding compound offormula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryland wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

In a special embodiment the invention relates to a process for thepreparation of a compound of formula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryland wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H,comprising the steps of protecting a compound of formula (7)

wherein X³ stands for a halogenwherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H, and wherein R¹⁵ and R¹⁶each independently stand for H, alkyl, or aryl,with PG-LG, wherein PG stands for a protecting group and wherein LGstands for a leaving group to form the corresponding compound of formula(6)

wherein X³, R⁹, R¹⁰, R¹¹ and R¹² are as defined herein and wherein PGstands for the protecting groupreacting the compound of formula (6) with a compound of formula (5)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing group and wherein R¹³ and R¹⁴ each independentlystand for H, alkyl or aryl,in a solvent in the presence of a Pd catalyst and a base to form thecorresponding compound of formula (4)

wherein R¹, R², R³, R⁴, R⁵ and R⁶, R⁹, R¹⁰, R¹¹ and R¹² and PG are asdefined hereinand deprotecting the compound of formula (4) by reaction of the compoundof formula (4) with an acid to form the corresponding compound offormula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryland wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

In yet another aspect, the invention relates to a compound of formula(1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryland wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

Preferably, in the compound of formula (1), R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

X³

In the compound of formula (7), X³ stands for halogen, for example Fl,I, Cl or Br, preferably Br.

R¹⁵ and R¹⁶

In the compound of formula (7), R¹⁵ and R¹⁶ each independently stand forH, alkyl, for example an alkyl of 1 to 6 carbon atoms, for examplemethyl, ethyl, t-butyl, n-propyl or isopropyl, preferably methyl orisopropyl, or a cyclic alkyl, for example of 4 to 8 carbon atoms; aryl,preferably phenyl. Preferably R¹⁵ and R¹⁶ both stand for H.

In the deprotecting step, the compound of formula (7) is reacted withPG-LG, wherein PG stands for a protecting group and wherein LG standsfor a leaving group, for example PG-LG stands for a 2-amino groupseparated by 2 to 6 carbon atoms, for example PG-LG stands for1,8-diamino naphthalene. When a reaction with PG-LG occurs, theprotecting group PG will be bound to the compound of formula (7).

The reaction conditions for the deprotecting step are in principle notcritical. For example, the temperature may be chosen—depending on thechoice of solvent—in the range of 100 to 150° C. The reaction ispreferably performed under atmospheric pressure (1 bar).

Examples of solvents that are suitable for the deprotecting step includebut are not limited to alcohols, for example methanol or ethanol;aromatic solvents, for example benzene, toluene or xylene; ethers, forexample tetrahydrofuran, dioxane or dimethoxyethane; amides, for exampledimethylformamide. Preferably, for the deprotecting step organicsolvents, such as toluene are used.

Preferably, the molar ratio of the compound of formula (7) to PG-LG isin the range from 1:1 to 1:3, for example the molar ratio of thecompound of formula (7) to PG-LG is about 1:1.6.

The compound of formula (7) is commercially available, from for exampleAldrich, but can also be synthesized using methods known in the art.

The protected compound of formula (6) is then reacted with a compound offormula (5)

R¹³ and R¹⁴

In the compound of formula (5), R¹³ and R¹⁴ each independently stand forH, alkyl, for example a cyclic alkyl or an acyclic alkyl, for example alinear alkyl, for example an alkyl having 1 to 6 C-atoms, for examplemethyl, ethyl, t-butyl, i-propyl or n-hexane; or for aryl, for examplephenyl.

Suitable solvents for the reaction of the compound of formula (6) withthe compound of formula (5) include but are not limited to alcohols, forexample methanol or ethanol; aromatic solvents, for example benzene,toluene or xylene; ethers, for example tetrahydrofuran, dioxane ordimethoxyethane; amides, for example dimethylformamide. Preferablyorganic solvents are used, more preferably aromatic solvents, morepreferably toluene. Mixtures of solvents, such as the solvents mentionedherein may also be used.

The Pd catalysts that can be used in the reaction of the compound offormula (6) with the compound of formula (5) are in principle all Pdcatalysts known to be suitable for Suzuki couplings. Preferably, a Pd(0)catalyst or a catalyst wherein Pd(0) is generated in situ by reductionof (more stable) Pd(II) compounds is used. Examples of Pd catalystsinclude tetrakis(triphenylphosphin)palladium ((Ph₃P)₄Pd), palladium (II)acetate (Pd(O₂CCH₃)₂ or Pd(Oac)₂), tris(dibenzylideneacetone)dipalladium(PD(dba)₂) and bis(triphenylphosphin)palladium dichloride (PPh₃)₂PdCl₂),1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II)(PdCl₂(dppf)), [1,2-bis(diphenylphosphino)ethane]dichloropalladium(II),(PdCl₂(dppe)), bis(tricyclohexyl phosphine)palladium(0),bis(triethylphosphine)palladium(II) chloride,bis(tri-t-butylphosphine)palladium(0),bis[1,2-bis(diphenylphosphino)ethane] palladium(0),bis[tri(o-tolyl)phosphine]palladium(II) chloride,trans-benzyl(chloro)bis(triphenylphosphine)palladium(II) or Pd on carbon(Pd/C).

Preferably as Pd catalyst, tetrakis(triphenylphosphin)palladium(Pd(PPh₃)₄) or Pd/C is used.

The base that can be used in the reaction of the compound of formula (6)with the compound of formula (5) can in principle be any base, forexample an inorganic or an organic base. Preferably an organic base isused in the preparation of the bridged bis-indenyl) ligand of formula(3), such as for example a quaternary ammonium salt, for example tetran-butylammoniumacetate or a tertiary amine, for example triethylamine(Et₃N). Other examples of suitable bases include but are not limited tosodium carbonate, sodium acetate, sodium tert-butoxide, potassiumcarbonate, potassium iodide, sodium iodide, potassium acetate, cesiumcarbonate, cesium fluoride, lithium hydroxide, sodium hydroxide, sodiumethoxide, potassium fluoride and potassium phosphate.

In principle, the reaction conditions for the reaction of compound (6)with compound (5) are not critical and the temperatures, pressures andreaction time known to be suitable for Suzuki couplings, may be used bythe person skilled in the art and optimal conditions can be found usingroutine experimentation. For example, the temperature may be from 60 to120° C., as at temperatures below 60° C., the reaction hardly proceedsand at temperatures of above 120° C., tarring may occur. Preferably, thetemperature is chosen to be at least 60, preferably at least 75 and/orat most 100, preferably at most 85° C. The pressure under which theprocess is performed is preferably atmospheric pressure (1 bar). Thereaction time may for example be in the range from 36 to 48 hours.

The concentration of the compound of formula (6) and of the compound offormula (5) is in principle not critical, but the volume of solvent mayfor example be in the range from 4-10 times, for example about 6.5 timesthat of the sum of the weight of the compound of formula (6) and thecompound of formula (5).

The step of deprotecting the compound of formula (4) to remove theprotecting group PG is performed with an acid. Examples of suitableacids for said deprotection include but are not limited to acidicresins, mineral acids and organic acids, such as sulphuric acid andphosphoric acid.

The person skilled in the art is aware of which solvents can be used forthe deprotection of the compound of formula (4). For example, the samesolvent as for the reaction of the compound of formula (6) with thecompound of formula (5) may be used, for example alcohols, for examplemethanol or ethanol; aromatic solvents, for example benzene, toluene orxylene; ethers, for example tetrahydrofuran, dioxane or dimethoxyethane;amides, for example dimethylformamide; or water. Preferably organicsolvents are used, more preferably aromatic solvents, more preferablytoluene. Mixtures of solvents, such as the solvents mentioned herein mayalso be used, for example a mixture of water and an aromatic solvent ora mixture of water with an alcohol such as ethanol.

The person skilled in the art knows at which temperature and pressuresto perform such deprotection, for example the temperature for thedeprotection may be selected in the range of 10 to 25° C. The pressureunder which the process is performed is preferably atmospheric pressure(1 bar).

Preferably, the deprotection of the compound of formula (4) is performedusing a molar ratio of acid to compound of formula (4) in the range from1:1 to 4:1, for example using excess of acid, for example in a molarratio of acid to compound of formula (4) of about 1.4:1.

Alternatively, the compound of formula (1) may be prepared using theprocess according to the invention further comprising the step ofpreparing a compound of formula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryland wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H,by a process comprising the step of reacting a compound of formula (9)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² are as definedherein and wherein X⁴ stands for a halogen with a compound of formula(10)B(OR¹⁷)₃  (10)wherein R¹⁷ stands for H or for an alkyl having 1 to 6 carbon atomsin the presence of magnesium and an acidto form the corresponding compound of formula (1).

The temperature for this process is preferably chosen in the range from15 to 35 C. The pressure chosen is preferably atmospheric pressure (1bar). The solvent chosen is preferably an organic solvent, for exampletetrahydrofuran (THF).

Preferably, the compound of formula (9) and the compound of formula (10)are used in a solvent, wherein the volume of solvent: the total weightof the compound of formula (9) and the compound of formula (10) ischosen in the ratio from 8:1-12:1. Preferably, the compound of formula(10) and the compound of formula (9) are used in a molar ratio of thecompound of formula (10) to the compound of formula (9) in the rangefrom 4:1 to 1:1, preferably about 2:1.

In another aspect, the invention relates to a process for thepreparation of a compound of formula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryland wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H,comprising the step of reacting a compound of formula (9)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² are as definedherein and wherein X⁴ stands for a halogen with a compound of formula(10)B(OR¹⁷)₃  (10)wherein R¹⁷ stands for H or for an alkyl having 1 to 6 carbon atomsin the presence of magnesium and an acidto form the corresponding compound of formula (1)X⁴

In the compound of formula (9), X⁴ stands for a halogen, for example Fl,Cl or Br, preferably for Br.

In this process, the compound of formula (9) is reacted with a compoundof formula (10)B(OR¹⁷)₃  (10)wherein R¹⁷ stands for H or for an alkyl having 1 to 6 carbon atoms, forexample methyl, n-butyl, propyl or isopropyl, in the presence ofmagnesium and an acid.

Examples of acids suitable for the reaction of the compound of formula(9) with the compound of formula (10) to form the corresponding compoundof formula (1) include but are not limited to inorganic acids, forexample HCl, mineral acids and acidic resins.

In another embodiment, the invention also relates to a process for thepreparation of the compound of formula (1), R⁷ and R⁸ form a ringtogether with the oxygen atoms to which they are bound. Specifically,the invention relates to a process according to the invention, furthercomprising the step of preparing the compound of formula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ form a ring together with the oxygen atoms to whichthey are boundand wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H,by a process comprising the steps of reacting a compound of formula (12)

wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H,and wherein X¹ and X² are each independently chosen from the group ofhalogens and preferably wherein X¹ and X² are not the samewith a compound of formula (5)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, anamine, a Si or B-containing group or a P-containing groupand wherein R¹³ and R¹⁴ each independently stand for H, alkyl or arylin a solvent in the presence of a Pd catalyst and a baseto form the corresponding compound of formula (13)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹, R¹² and X² are as definedhereinreacting the compound of formula (13) with a compound of formula (14)

in a solvent, in the presence of a Nickel (II) or Nickel (0) catalyst, aligand for the Nickel (II) or Nickel (0) catalyst and a base to form thecorresponding compound of formula (1),

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ form a ring together with the oxygen atoms to whichthey are bound and wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

In another aspect, the invention relates to a process for thepreparation of a compound of formula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ form a ring together with the oxygen atoms to whichthey are bound comprising the steps of reacting a compound of formula(12X)

wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H,and wherein X¹ and X² are each independently chosen from the group ofhalogens and preferably wherein X¹ and X² are not the samewith a compound of formula (5)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupand wherein R¹³ and R¹⁴ each independently stand for H, alkyl or aryl,in a solvent in the presence of a Pd catalyst and a baseto form the corresponding compound of formula (13)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹, R¹² and X² are as definedhereinreacting the compound of formula (13) with a compound of formula (14X)

in a solvent, in the presence of a Nickel (II) or Nickel (0) catalyst, aligand for the Nickel (II) or Nickel (0) catalyst and a base to form thecorresponding compound of formula (1X).

In yet another aspect, the invention relates to the novel compound offormula (1X)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupand wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

Preferably, the invention relates to the compound of formula (1X),wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² all stand for H.

X¹ and X²

In the compound of formula (12), X¹ and X² are each independently chosenfrom the group of halogens, for example F, Cl, Br, preferably Cl and Br.Preferably X¹ and X² are not the same. Preferably, X¹ stands for Br andX² stands for Cl.

The Pd catalysts that can be used in the reaction of compound of formula(12) with the compound of formula (5) are in principle all Pd catalystsknown to be suitable for Suzuki couplings. Preferably, a Pd(0) catalystor a catalyst wherein Pd(0) is generated in situ by reduction of (morestable) Pd(II) compounds is used. Examples of Pd catalysts includetetrakis(triphenylphosphin)palladium ((Ph₃P)₄Pd), palladium (II) acetate(Pd(O₂CCH₃)₂ or Pd(Oac)₂), tris(dibenzylideneacetone)dipalladium(PD(dba)₂) and bis(triphenylphosphin)palladium dichloride (PPh₃)₂PdCl₂),1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II)(PdCl₂(dppf)), [1,2-bis(diphenylphosphino)ethane]dichloropalladium(II),(PdCl₂(dppe)), bis(tricyclohexyl phosphine)palladium(0),bis(triethylphosphine)palladium(II) chloride,bis(tri-t-butylphosphine)palladium(0),bis[1,2-bis(diphenylphosphino)ethane] palladium(0),bis[tri(o-tolyl)phosphine]palladium(II) chloride,trans-benzyl(chloro)bis(triphenylphosphine)palladium(II).

Preferably the Pd catalyst is chosen from the group of PdCl₂(dppf),PdCl₂(dppe), bis(tricyclohexyl phosphine)palladiume(0),bis(triethylphosphine)palladium(II) chloride,bis(tri-t-butylphosphine)palladium(0),bis[1,2-bis(diphenylphosphino)ethane] palladium(0),bis[tri(o-tolyl)phosphine]palladium(II) chloride andtrans-Benzyl(chloro)bis(triphenylphosphine)palladium(II).

The base that can be used in the reaction of the compound of formula(12) with the compound of formula (5) can in principle be any base, forexample an inorganic or an organic base. Preferably an organic base isused in the preparation of the bridged bis-indenyl) ligand of formula(3), such as for example a quaternary ammonium salt, for example tetran-butylammoniumacetate or a tertiary amine, for example triethylamine(Et₃N) or tetrabutyl ammonium hydroxide. Preferably tetrabutyl ammoniumhydroxide is used as the base in the reaction of the compound of formula(12) with the compound of formula (5). Other examples of suitable basesinclude but are not limited to sodium tert-butoxide, potassiumcarbonate, lithium hydroxide, sodium hydroxide, sodium ethoxide,potassium fluoride and potassium phosphate.

Other examples of suitable bases include but are not limited to sodiumcarbonate, sodium acetate, sodium tert-butoxide, potassium carbonate,potassium iodide, sodium iodide, potassium acetate, cesium carbonate,cesium fluoride, lithium hydroxide, sodium hydroxide, sodium ethoxide,potassium fluoride and potassium phosphate.

Suitable solvents for the reaction of the compound of formula (12) withthe compound of formula (5) include but are not limited to alcohols, forexample methanol or ethanol; aromatic solvents, for example benzene,toluene or xylene; ethers, for example tetrahydrofuran, dioxane ordimethoxyethane; amides, for example dimethylformamide or water that ispreferably substantially free of oxygen. Preferably organic solvents areused, more preferably aromatic solvents, more preferably toluene.Mixtures of solvents, such as the solvents mentioned herein may also beused.

In principle, the reaction conditions for the reaction of the compoundof formula (12) or of the compound of formula (12X) with the compound offormula (5) are not critical and the temperatures, pressures andreaction time known to be suitable for Suzuki couplings, may be used bythe person skilled in the art and optimal conditions can be found usingroutine experimentation. For example, the temperature may be from 60 to120° C., as at temperatures below 60° C., the reaction hardly proceedsand at temperatures of above 120° C., tarring may occur. Preferably, thetemperature is chosen to be at least 60, preferably at least 75 and/orat most 100, preferably at most 85° C. The pressure under which theprocess is performed is preferably atmospheric pressure (1 bar). Thereaction time may for example be in the range from 36 to 48 hours.

The molar ratio of the compound of formula (12) or of the compound offormula (12X) to the compound of formula (5) is preferably chosen in therange from 1:1 to 1:3, for example in a molar ratio of about 1:1.2.

The concentration of the compound of formula (12) or of the compound offormula (12X) and of the compound of formula (5) is in principle notcritical, but the volume of solvent may for example be in the range from3-5 times, for example about 4.4 times that of the sum of the weight ofthe compound of formula (12) or the compound of formula (12X) and thecompound of formula (5).

The compound of formula (13) that is produced in the reaction of thecompound of formula (12) or of the compound of formula (12X) with thecompound of formula (5) is then reacted with the compound of formula(14) in the presence of a Nickel (II) or Nickel (0) catalyst, a ligandfor the Nickel (II) or Nickel (0) catalyst and a base, for exampletriethylamine.

Examples of ligands for the nickel catalyst include but are not limitedto triphenylphosphine (PPh₃), 1,3-Bis(diphenylphosphino)propane (dppp),1,2-Bis(diphenylphosphino)ethane (dope),1,2-Bis(dimethylphosphino)ethane (dmpe),1,4-Bis(diphenylphosphino)butane (dppb).

Examples of Nickel (II) or Nickel (0) catalyst and ligand combinationsthat are suitable for the reaction of the compound of formula (13) withthe compound of formula (14) include but are not limited tobis(1,5-cyclooctadiene) nickel(0) (Ni(COD)₂), nickel(II) acetylacetonate(Ni(acac)2), Dichloro[1,3-bis(diphenylphosphino)propane]nickel(NiCl2-dppp), bis(Acetonitrile) dichloro nickel(II)(Ni(MeCN)2Cl2),allylchloro-[1,3-bis-(diisopropylphenyl)-imidazole-2-ylidene] nickel(II)((iPr)Ni(allyl)Cl), bis(tricyclohexyl phosphine) dichloro nickel(II)(NiCl2(PCy3)2), nickel(II) chloride hexahydrate (NiCl2 hexahydrate),nickel(II) bromide hexahydrate (NiBr2 hexahydrate),bis(triphenylphosphine)nickel(II)chloride,tetrakis(triphenylphosphine)nickel(0) and1,2-bis(dicyclohexylphosphino)ethane nickel(II) chloride.

Examples of bases that are suitable for the reaction of the compound offormula (13) with the compound of formula (14) include but are notlimited to organic and inorganic bases, for example trimethyl amine,potassium carbonate, sodium carbonate, sodium acetate, potassium iodide,sodium iodide, potassium acetate, lithium hydroxide, cesium carbonate,cesium fluoride, sodium hydroxide, sodium ethoxide, potassium fluoride,potassium phosphate, tetra n-butylammoniumacetate, tetrabutyl ammoniumhydroxide, tetrabutyl ammonium hydroxide, sodium tert-butoxide,potassium carbonate or lithium hydroxide.

Preferably, the solvent that is used for the reaction of the compound offormula (13) with the compound of formula (14) or the compound offormula (14X) is an organic solvent, such as for example an alcohol, forexample methanol or ethanol, an aromatic solvent, for example toluene;an ether or an amide. Preferably the solvent that is used for thereaction of the compound of formula (13) with the compound of formula(14) or the compound of formula (14X) is methanol or ethanol.

The temperature for the reaction of the compound of formula (13) withthe compound of formula (14) or the compound of formula (14X) ispreferably chosen in the range from 40 to 100° C. The reaction ispreferably performed under atmospheric pressure (1 bar)

Preferably the molar ratio of the compound of formula (13) to thecompound of formula (14) or the compound of formula (14X) is chosen inthe range from 1:1 to 1:3, for example about 1:1.15. The concentrationof the compound of formula (13) and of the compound of formula (14) orthe compound of formula (14X) is in principle not critical, but thevolume of solvent may for example be in the range from 3-5 times, forexample about 4.4 times that of the sum of the weight of the compound offormula (13) and the compound of formula (14) or the compound of formula(14X).

The compound of formula (2) can be prepared using methods known in theart, for example as described in U.S. Pat. No. 6,342,622, herebyincorporated by reference.

For the syntheses as described herein, the separation of products fromunreacted reactants and the purification of intermediates in thesynthetic process is generally not required. Preferably, however, thecompound of formula (13) is purified, for example using a high vacuumdistillation before it is reacted with the compound of formula (14) orthe compound of formula (14X) to form the corresponding compound offormula (1) respectively the compound of formula (1X).

The process of the invention may further comprise the step of convertingthe compound of formula (3)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H, ahydrocarbon radical having 1-20 C-atoms, a halide, an alkoxy grouphaving 1-6 C-atoms, an alkylsulphide, an amine, a Si or B-containinggroup or a P-containing groupwherein R⁷ and R⁸ each independently stand for H, or an alkyl or aryl orwherein R⁷ and R⁸ may form a ring together with the oxygen atoms towhich they are boundand wherein R⁹, R¹⁰, R¹¹ and R¹² all stand for H, into the correspondingmetallocene complex of formula (15)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² are as definedhereinwherein M stands for a transition metal from the group of lanthanides orfrom group 3, 4, 5 or 6 of the Periodic System of Elements,wherein Q stands for an anionic ligand to M,and wherein k is an integer and stands for the number of anionicligands.

In the metallocene complex of formula (15)

R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² are as defined herein, Mstands for a transition metal from the group of lanthanides or fromgroup 3, 4, 5 or 6 of the Periodic System of Elements, Q stands for ananionic ligand to M, and k is an integer and stands for the number ofanionic ligands.

For example, a metallocene complex of formula (15) may be prepared in atwo-step procedure as for example described in EP1059300A1, herebyincorporated by reference. Specifically in paragraph [0036] ofEP1059300A1, it is described that the compound of formula (3) may firstbe converted into its dianion using for example an organometalliccompound, an amine, a metal hydride, an alkaline earth metal or analkaline earth metal. Organolithium, organomagnesium and organosodiumcompound may for example be used, but also sodium or potassium.Organolithium compounds, such as methyl-lithium or n-butyllithium areparticularly suitable for converting the compound of formula (3) intoits dianion.

In paragraph [0037] of EP1059300A1, it is described that the dianioncorresponding to a bridged bis(indenyl) ligand may be converted into thecorresponding metallocene complex by transmetalation with a compound oftransition metal M, wherein M is as defined herein. See for exampleEP-A-420436 or EP-A-427697. The process described in NL-A-91011502 isparticularly suitable. Examples of compounds of transition metal Minclude but are not limited to TiCl₄, ZrCl₄, HfCl₄, Zr(OBu)₄ andZr(OBu)₂Cl₂. The transmetalation may be carried out as in NL-A-91011502in a solvent or in a combination of solvents that weakly coordinate totransition metals from the groups 3, 4, 5, or 6 of the Periodic Systemof Elements with at most 1 mole equivalent, relative to the transitionmetal compound started from, of a Lewis base of which the conjugatedacid has a pK_(a) greater than −2.5. Examples of solvents/dispersants(pK_(a) of conjugated acid=<−2.5) that may suitably be used in suchtransmetalation include but are not limited to ethoxyethane,dimethoxyethane, isopropoxyisopropane, n-propoxy-n-propane,methoxybenzene, methoxymethane, n-butoxy-n-butane, ethoxy-n-butane anddioxane. Part of the reaction medium used for the transmetalation mayconsist of hydrocarbons (hexane and the like).

In particular, the invention further relates to a process for thepreparation of a compound of formula (15), wherein the compound offormula (3) is converted into its corresponding dianion using anorganometallic compound, an amine, a metal hydride, an alkaline earthmetal or an alkaline earth metal and wherein the formed dianion istransmetalated with a compound of transition metal M, to form thecorresponding metallocene complex of formula (15).

Transition Metal M

The transition metal M is selected from the lanthanides or from group 3,4, 5 or 6 of the Periodic System of Elements. The Periodic System ofElements is understood to be the new IUPAC version as printed on theinside cover of the Handbook of Chemistry and Physics, 70th edition, CRCPress, 1989-1990.

Preferably, M stands for Ti, Zr, Hf, V or Sm, more preferably for Ti,Zr, Hf, more preferably for preferably for Zr or Hf, even morepreferably for Zr. Complexes of formula (15), wherein M stands for Zr orHf metallocene may suitably be used as catalysts in the synthesis ofpolyethylene or the synthesis of polypropylene. Please note that theexpression ‘synthesis/preparation of polyethylene’ referred herein isdefined as homopolymerization or copolymerization of ethylene with oneor more α-olefins having 3-12 C-atoms and optionally one or morenon-conjugated dienes.

Anionic Ligand Q

Q stands for an anionic ligand to the transition metal M. The anionicligand may comprise one or more uni- or polyvalent anionic ligands.Examples of such ligands include but are not limited to a hydrogen atom,a halogen atom, an alkyl group, an aryl group, an aralkyl group, analkoxy group, an aryloxy group and a group with a heteroatom chosen fromgroup 14, 15 or 16 of the Periodic System of Elements, such as forexample an amine group or amide group; a sulphur containing group, forexample sulphide or sulphite; a phosphorus containing group, for examplephosphine or phosphite.

Q may also be a monoanionic ligand bonded to the transition metal M viaa covalent metal-carbon bond and which is additionally capable tonon-covalently interact with M via one of more functional groups. Thefunctional group mentioned above can be one atom, but also a group ofatoms connected together. The functional group is preferably an atom ofgroup 17 of the Periodic Table of Elements or a group containing one ormore elements from groups 15, 16 or 17 of the Periodic Table ofElements. Examples of functional groups are F, Cl, Br, dialkylamino andalkoxy groups.

Q may for example be a phenyl group in which at least one of theortho-positions is substituted with a functional group capable ofdonating electron density to the transition metal M. Q may also be amethyl group in which one or more of the alpha-positions is substitutedwith a functional group capable of donating electron density to thetransition metal M. Examples of methyl groups substituted in one or moreof the alpha-positions are benzyl, diphenylmethyl, ethyl, propyl andbutyl substituted with a functional group capable of donating electrondensity to the transition metal M. Preferably at least one of theortho-positions of a benzyl-group is substituted with a functional groupcapable of donating electron density to the transition metal M.

Examples of these Q groups include, but are not limited to:2,6-difluorophenyl, 2,4,6-trifluorophenyl, pentafluorophenyl,2-alkoxyphenyl, 2,6-dialkoxyphenyl, 2,4,6-tri(trifluoromethyl)phenyl,2,6-di(trifluoromethyl)phenyl, 2-trifluoromethylphenyl,2-(dialkylamino)benzyl and 2,6-(dialkylamino)phenyl.

Q may for example stand for a mono-anionic ligand, for example formethyl of Cl, preferably for Cl.

Integer k

The number of Q groups in the metallocene complex of formula (15)(represented by the integer k in formula (6)) is determined by thevalence of the transition metal M and the valence of the Q groups. Inthe metallocene complex of formula (6), k is equal to the valence of Mminus 2 divided by the valence of Q. For example, in case M stands forZr and Q stands for Cl, k is 2.

In a preferred embodiment, the metallocene complex of formula (15) is[2,2′-bis(2-indenyl)biphenyl]ZrCl₂.

The metallocene complex of formula (15) may be used, optionally in thepresence of a cocatalyst for the polymerization of one or moreα-olefins, preferably for the polymerization of ethylene, for example insolution or suspension polymerization of ethylene.

The α-olefin(s) is/are preferably chosen from the group comprisingethylene, propylene, butene, pentene, hexene, heptene and octene, whilemixtures can also be used. More preferably, ethylene and/or propyleneis/are used as α-olefin. The use of such α-olefins leads to theformation of crystalline polyethylene homopolymers and copolymers ofboth low and high density (HDPE, LDPE, LLDPE, etc.), and polypropylenehomopolymers and copolymers (PP and EMPP). The monomers needed for suchproducts and the processes to be used are known to the skilled in theart.

The metallocene complex of formula (15) is also suitable for thepreparation of amorphous or rubbery copolymers based on ethylene andanother α-olefin. Propylene is preferably used as the other α-olefin, sothat EPM rubber is formed.

Details of such use and examples of cocatalysts may be found in EP1059300 A1, paragraphs [0038]-[0057]; hereby incorporated by reference.

Cocatalyst

The cocatalyst for the polymerization of one or more α-olefins can be anorganometallic compound. The metal of the organometallic compound can beselected from group 1, 2, 12 or 13 of the Periodic Table of Elements.Suitable metals include sodium, lithium, zinc, magnesium, and aluminium,preferably aluminium. At least one hydrocarbon radical is bondeddirectly to the metal to provide a carbon-metal bond. The hydrocarbongroup used in such compounds preferably contains 1-30, more preferably1-10 carbon atoms. Examples of suitable compounds include, amyl sodium,butyl lithium, diethyl zinc, butyl magnesium chloride, and dibutylmagnesium. Preference is given to organoaluminium compounds, including,for example and without limitation, the following: trialkyl aluminiumcompounds, such as triethyl aluminium and tri-isobutyl aluminium; alkylaluminium hydrides, such as diisobutyl aluminium hydride; alkylalkoxyorganoaluminium compounds; and halogen-containing organoaluminiumcompounds, such as diethyl aluminium chloride, diisobutyl aluminiumchloride, and ethyl aluminium sesquichloride. Preferably, aluminoxanesare selected as the organoaluminium compound. Most preferably,methylaluminoxane (MAO) is used as the cocatalyst.

The aluminoxanes can also be aluminoxanes containing a low amount oftrialkylaluminium; preferably 0.5 to 15 mol % trialkylaluminium. In thiscase the amount of trialkylaluminium is more preferably 1-12 mol %trialkylaluminium.

In addition or as an alternative to the organometallic compounds as thecocatalyst, the polymerization may be performed in the presence of acompound which contains or yields in a reaction with the metallocenecomplex of formula (15), a non-coordinating or poorly coordinatinganion. Such compounds have been described for instance in EP-A-426,637,the complete disclosure of which is incorporated herein by reference.Such an anion is bonded sufficiently unstably such that it is replacedby an unsaturated monomer during the copolymerization. Such compoundsare also mentioned in EP-A-277,003 and EP-A-277,004, the completedisclosures of which are incorporated herein by reference. Such acompound preferably contains a friaryl borane or a tetraaryl borate oran aluminium or silicon equivalent thereof. Examples of suitablecocatalyst compounds include, without limitation, the following:

-   -   dimethyl anilinium tetrakis (pentafluorophenyl) borate        [C₆H₅N(CH₃)₂H]+[B(C₆F₅)₄]⁻;    -   dimethyl anilinium bis (7,8-dicarbaundecaborate)-cobaltate        (III);    -   tri(n-butyl)ammonium tetraphenyl borate;    -   triphenylcarbenium tetrakis (pentafluorophenyl) borate;    -   dimethylanilinium tetraphenyl borate;    -   tris(pentafluorophenyl) borane; and    -   tetrakis(pentafluorophenyl) borate.

As described for instance in EP-A-500,944, the complete disclosure ofwhich is incorporated herein by reference, the reaction product of ahalogenated transition metal complex and an organometallic compound,such as for instance triethyl aluminium (TEA), can also be used.

The molar ratio of the cocatalyst relative to the transition metalcomplex (metallocene complex of formula (6)), in case an organometalliccompound is selected as the cocatalyst, usually is in a range of fromabout 1:1 to about 10,000:1, and preferably is in a range of from about1:1 to about 2,500:1. If a compound containing or yielding anon-coordinating or poorly coordinating anion is selected as cocatalyst,the molar ratio usually is in a range of from about 1:100 to about1,000:1, and preferably is in a range of from about 1:2 to about 250:1.

The metallocene complex of formula (15) as well as the cocatalyst may beused in the polymerizations of α-olefins as a single component or as amixture of several components. As is known to the person skilled in theart, a mixture may for instance be desired where there is a need toinfluence the molecular properties of the polymer, such as molecularweight and in particular molecular weight distribution.

The metallocene complex of formula (15) can be used supported as well asnon-supported. The supported catalysts are used mainly in gas phase andslurry processes. The carrier used may be any carrier known as carriermaterial for catalysts, for instance silica, alumina or MgCl₂.Preferably, the carrier material is silica.

Support

The catalyst complex of formula (15) can be used supported as well asnon-supported. The carrier used may be any carrier known as carriermaterial for catalysts. For instance, the support in the catalystcomposition of the present invention can be an organic or inorganicmaterial and is preferably porous. Examples of organic material arecross-linked or functionalized polystyrene, PVC, cross-linkedpolyethylene. Examples of inorganic material are silica, alumina,silica-alumina, inorganic chlorides such as MgCl₂, talc and zeolite.Mixtures of two or more of these supports may also be used. Thepreferred particle size of the support is from 1 to 120 micrometers,preferably of from 20 to 80 micrometers and the preferred averageparticle size is from 40 to 50 micrometers.

The preferred support is silica. The pore volume of the support ispreferably of from 0.5 to 3 cm³/g. The preferred surface area of thesupport material is in the range of from 50 to 500 m²/g. The silica usedin this invention is preferably dehydrated prior to being used toprepare the catalyst composition.

Therefore, the process of the present invention may further comprise thestep(s) of

-   -   combining in a solvent a support material, the catalyst complex        of formula (15) (also referred to herein as the compound of        formula (15)) to form the supported catalyst and    -   optionally drying the supported catalyst.

Further details on the synthesis of the (supported) catalyst can befound in EP1059300A1, hereby incorporated by reference or inWO2013/097936A1, hereby also incorporated by reference.

Polymerization of α-olefins can be effected in a known manner, in thegas phase as well as in a liquid reaction medium. In the latter case,both solution and suspension polymerization are suitable, while thequantity of transition metal to be used generally is such that itsconcentration in the dispersion agent amounts to 10⁻⁸-10⁻⁴ mol/l,preferably 10⁻⁷-10⁻³ mol/l.

The production processes of LLDPE are summarised in “Handbook ofPolyethylene” by Andrew Peacock (2000; Dekker; ISBN 0824795466) at pages43-66.

The polymerizations using the metallocene complex of formula (15) willhereafter be explained in further detail with reference to apolyethylene preparation known per se, which is representative of theα-olefin polymerizations meant here. For the preparation of otherpolymers on the basis of an α-olefin, the reader is expressly referredto the multitude of publications on this subject.

The preparation (polymerization) of polyethylene referred to herein isdefined as homopolymerization or copolymerization of ethylene with oneor more α-olefins having 3-12 carbon atoms and optionally one or morenon-conjugated dienes. The α-olefins that are particularly suitableinclude propylene, butane, for example 1-butene; hexane, for example1-hexene; and octene. Suitable dienes include for instance 1,7-octadieneand 1,9-decadiene.

Any liquid that is inert relative to the catalyst system (themetallocene complex of formula (15) and the optional cocatalyst) may beused as dispersion agent in the polymerization. One or more saturated,straight or branched aliphatic hydrocarbons, such as butanes, pentanes,hexanes, heptanes, pentamethyl heptane or mineral oil fractions such aslight or regular petrol, naphtha, kerosine or gas oil are suitable forthat purpose. Aromatic hydrocarbons, for instance benzene and toluene,can be used, but because of their cost as well as on account of safetyconsiderations, it will be preferred not to use such solvents forproduction on a technical scale. In polymerization processes on atechnical scale, it is preferred therefore to use as solvent thelow-priced aliphatic hydrocarbons or mixtures thereof, as marketed bythe petrochemical industry. If an aliphatic hydrocarbon is used assolvent, the solvent may yet contain minor quantities of aromatichydrocarbon, for instance toluene. Thus, if for instance methylaluminoxane (MAO) is used as cocatalyst, toluene can be used as solventin order to supply the MAO in dissolved form to the polymerizationreactor. Drying or purification is desirable if such solvents are used;this can be done without problems by the average person skilled in theart.

A solution polymerization is preferably carried out at temperaturesbetween 150° C. and 250° C.; in general, a suspension polymerizationtakes place at lower temperatures, preferably below 100° C.

The polymer solution resulting from the polymerization can be worked upby a method known per se. In general the catalyst system is de-activatedat some point during the processing of the polymer. The deactivation isalso effected in a manner known per se, e.g. by means of water or analcohol. Removal of the catalyst system residues can usually be omittedwhen the quantity of metallocene complex of formula (15) in the polymer,in particular the content of halogen and transition metal is very low.

Polymerization can be effected at atmospheric pressure, but also at anelevated pressure of up to 500 MPa, continuously or discontinuously. Ifthe polymerization is carried out under pressure, the yield of polymercan be increased additionally, resulting in an even lower catalystresidue content. Preferably, the polymerization is performed atpressures between 0.1 and 25 MPa. Higher pressures, of 100 MPa andupwards, can be applied if the polymerization is carried out inso-called high-pressure reactors. In such a high-pressure process themetallocene complex of formula (15) can also be used with good results.

The polymerization can also be performed in several steps, in series aswell as in parallel. If required, the catalyst composition, temperature,hydrogen concentration, pressure, residence time, etc. may be variedfrom step to step. In this way it is also possible to obtain productswith a wide molecular weight distribution.

Although the invention has been described in detail for purposes ofillustration, it is understood that such detail is solely for thatpurpose and variations can be made therein by those skilled in the artwithout departing from the spirit and scope of the invention as definedin the claims.

It is further noted that the invention relates to all possiblecombinations of features described herein, preferred in particular arethose combinations of features that are present in the claims.

It is further noted that the term ‘comprising’ does not exclude thepresence of other elements. However, it is also to be understood that adescription on a product comprising certain components also discloses aproduct consisting of these components. Similarly, it is also to beunderstood that a description on a process comprising certain steps alsodiscloses a process consisting of these steps.

The invention is now elucidated by way of the following examples,without however being limited thereto.

Comparative Experiments Process for Synthesis of[2,2′-Bis(2-indenyl)biphenyl] from Ortho-Bromo-(2-indenyl)Benzene (OBPI)or Ortho-Iodo-(2-indenyl)Benzene (OIPI)

Reaction-1:

Procedure:

In 10 ml round bottom flask (RBF), OBPI (0.10 g), Ni(COD)₂ (0.05 g) andDMF (5 ml) were added. The mixture was slowly stirred and heated up to100° C. for 2 hrs. Then a sample of the solution was submitted for HPLCanalysis. The HPLC result showed the formation of phenyl indene(impurity) and presence of unreacted OBPI. Not even traces of[2,2′-Bis(2-indenyl)biphenyl] (the desired product) formation could bedetected. The same reaction was carried out with OIPI instead of OBPIbut the desired product was again not obtained.

Reaction-2:

Procedure:

In a 25 ml RBF, OBPI (0.5 g), 10 ml THF were added and cooled to −40° C.Then n-BuLi (2.0 ml) was added slowly. During this addition, temperatureraised up to −35° C. After addition, the solution maintained at −40° C.for 30 min and then slowly the temperature was raised up to 0° C. andwater (5 ml) was added slowly. Then Dichloromethane (10 ml) was added.Two phases were separated and the organic phase was dried over sodiumsulphate. The solvent was then finally removed by distillation usingrotary evaporator. The residue submitted for HPLC analysis. The HPLCresult did show that instead of desired product only phenyl indene(impurity) was formed.

Reaction-3:

Procedure:

To a 50 ml RBF, OIPI (0.1 g), NiBr₂ (0.68 g), PPh₃ (0.329 g), Zn (0.02g) and DMF (10 ml) were added. The reaction mass purged with nitrogenand heated up to 110° C. for overnight. The progress of reaction wasmonitored by TLC. The formation of desired product was found. However, asample submitted for HPLC analysis showed that only a very low amount ofdesired product was formed (3.33%).

The reaction above was also tried with different temperatures (50° C.and 80° C.) and different catalyst compositions (NiCl₂ and Pd(PPh₃)₄)also. But results showed that only 3-4% product formation and/orformation of impurities (phenyl indene)

Reaction-4:

Procedure:

In a 50 ml sealed tube, OIPI (0.1 g) was added and heated up to 220° c.The reaction was monitored with TLC. After 16 hours, the desired productwas formed. Then a sample was submitted for HPLC. The HPLC analysis didhowever show that only 5% product was formed.

The comparative experiments above show that coupling of OBPI and OIPIleads to a poor yield for the desired product as well as to theformation of other compounds (impurities).

EXAMPLES ACCORDING TO THE PRESENT INVENTION Example 1. Preparation ofthe Compound of Formula (1), Wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹ and R¹² all Stand for H; Method 1

Synthesis of the Compound of Formula (6):

The compound of formula (7) (10 g, 49.79 mmol), 1,8-diamino naphthalene(8.66 g, 57.77 mmol) and Toluene (200 ml) were charged into a 500 mlfour neck round bottom flask. The resulting solution was refluxedovernight and then checked with thin layer chromatography (TLC). The TLCshowed that the reaction was complete. After this, the reaction wascooled to room temperature, water (50 ml) was added and the layers wereseparated. The organic layer was washed with dilute H₂SO₄ (10%, 50 ml)and the resulting layers were separated. Again the organic layer waswashed with saturated sodium chloride solution (100 ml), the layers wereseparated after which the organic layer was dried over sodium sulphateand the solvent was removed by using Rota evaporator, residuecrystallized in Hexane.

Wt.: 10.05 g (HPLC: 99.10%), Yield: 63%

Synthesis of the Compound of Formula (4):

The above synthesized compound-3 (10.05 g, 31.11 mmol), 2-indenylboronic acid (5.97 g, 37.33 mmol), Tetra butyl ammonium hydroxide (1M inmethanol, 94.5 ml, 37.33 mmol) [Pd(PPh₃)₄](approx 300 mg) and Toluene(100 ml) were charged into a 500 ml four neck flask. The resultingsolution was heated to reflux (77-78° C.) for 4 hrs. and then checkedwith TLC. TLC showed a completion of the reaction, so the reaction wascooled to 5° C. and dilute HCL (10%, 75 ml) and Dichloromethane (100 ml)were added. The obtained layers were separated and the organic layer waswashed with saturated sodium chloride. Subsequently, the organic layerwas dried over sodium sulphate and the remaining solvent was removed byRota evaporator and the residue crystallized in Hexane.

Wt.: 6.432 g (HPLC: 86.55%), Yield: 60.6%

Synthesis of the Compound of Formula (1):

The above synthesized compound of formula (4) (6.432 g, 17.95 mmol) andTHF (65 ml) were charged into a 250 ml four neck flask, stirringstarted. Into the resulting solution, dilute H₂SO₄ (1 M, 20 ml) wasslowly added. During addition, the temperature was raised from 15° C. to25° C. After the addition, the reaction was stirred for 1 hr and thenchecked with TLC. TLC showed a completion of the reaction, so into theresulting solution Dichloromethane (50 ml) was added. The obtainedlayers were separated, after which the organic layer was washed withsaturated sodium chloride solution, the solvent was distilled out byRota evaporator and the residue was crystallized in Hexane.

Wt.: 3.216 g (HPLC: 90%), Yield: 76%

The process of this example 1 is also illustrated by the below Scheme 1.

In Scheme 1, a compound of formula (7), wherein X³ stands for Br,wherein R⁹, R¹⁰, R¹¹, R¹², R¹⁵ and R¹⁶ all stand for H is protected withPG-L (1,8,-diamino naphthalene) to form the corresponding compound offormula (6). The compound of formula (6) is then reacted with thecompound of formula (5), wherein R¹, R², R³, R⁴, R⁵, R⁶, R¹³ and R¹⁴ allstand for H, in a solvent (toluene) in the presence of the Pd catalyst(Pd(PPh₃)₄) and the base tetrabutylammonium hydroxide to form thecorresponding compound of formula (4) after which the compound offormula (4) is deprotected by reaction of the compound of formula (4)with the mild sulphuric acid to form the corresponding compound offormula (1)

Example 2. Preparation of the Compound of Formula (1), wherein R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² all Stand for H; Method 2

In a 50 ml four neck flask the following components were charged Mgturning (0.224 g, 9.22 mmol), tetrahydrofuran (THF) (15 ml), Tri methylborate (3.04 g, 11.07 mmol), Ortho-Bromo-(2-indenyl)Benzene (OBPI) (1 g,3.69 mmol) and 1, 2-Dibromo ethane (2-3 drops). The resulting solutionwas heated up to 35° C. and maintained at this temperature for 1 hr.Then it was checked with TLC. TLC showed complete consumption ofstarting material. Therefore, the heating was stopped, the reaction wascooled down to room temperature, the solution poured into dilute HCL(5%, 25 ml), Dichloromethane (25 ml) was added. The resulting mixturewas stirred for 10 minutes and the formed layers were separated. Theorganic layer was dried over sodium sulphate and the solvent recoveredby Rota evaporator. The residue was washed with Hexane (25 ml) to removePhenyl indene.

Wt.: 250 mg (HPLC: 91%), Yield: 28.7%

The process of example 2 is also illustrated by the process in scheme 2.

In Scheme 2, a compound of formula (9), wherein R¹, R², R³, R⁴, R⁵, R⁶,R⁹, R¹⁰, R¹¹, R¹² all stand for H and wherein X⁴ stands for Br isreacted with the compound of formula (10), wherein R¹⁷ stands for H inthe presence of magnesium and an acid to form the corresponding compoundof formula (1).

Example 3. Preparation of 2,2′-bis(2-indenyl) biphenyl

The compound of formula (1), wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹ and R¹² all stand for H (1 g, 4.2 mmol), Tetra butyl ammoniumhydroxide (1M solution in methanol, 5.5 ml, 5.5 mmol), the compound offormula (2), wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹ and R¹² allstand for H and wherein X⁵ stands for Br (1.37 g, 5.1 mmol), Pd(PPh₃)₄(catalyst, 90 mg) and 15 ml of toluene were charged in 50 ml four neckround bottom flask. Resulted solution was refluxed (77-78° C.) for 1hrs. and the product immediately started to precipitate out. Refluxcontinued further 1 hrs. and then checked TLC, it was showing completionof reaction. So the reaction was cooled to 0-5° C., HCl (10%, 10 ml) wasadded, stirred for 5 minutes, the solution was filtered, residue waswashed with water and dried in an oven, to obtain 1.31 g (97% purity byHPLC, 82% yield). However, instead of Pd(PPh₃)₄, Pd/C may also beemployed.

The process of example 3 is also illustrated by Scheme 3 below:

In Scheme 3, a compound of formula (1) (2-boronic acid phenyl indene),wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² all standfor H and a compound of formula (2) (2-bromo phenyl indene), wherein R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁰, R¹¹ and R¹² all stand for H and wherein X⁵stands for Br are reacted in the presence of a Pd catalyst and a base toform the corresponding compound of formula (3).

Example 4. Preparation of the Compound of Formula (1), Wherein R¹, R²,R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² all Stand for H and Wherein R⁷ andR⁸ Form a Pinacolyl Ring Together with the Oxygen Atoms to which theyare Bound (=Building Block X)

Step 1: 2-indenyl boronic acid (10 g, 56.7 mmol), and1-bromo-2-chlorobenzene (13.03 g, 68.01 mmol), Tetra butyl ammoniumhydroxide (1M in Methanol, 68 ml, 68.04 mmol), Tetrakis palladiumtriphenyl phosphine (400 mg) and Toluene (100 ml) charged in to 500 mlfour neck flask. Resulted solution was heated to reflux (78° C.-80° C.)and reflux continued for further 5 hrs. Then sample submitted for HPLC,it was showing completion of reaction. So heating stopped, reactioncooled down 5° C. temperature. Then added dilute HCL (10%, 75 ml),stirred for 10 minutes, separated layers, organic layer washed withdilute sodium chloride solution and dried over Sodium sulphate. Solventremoved by Rota evaporator to afford the crude product, 2-chlorophenylindene (14.2 g, purity by HPLC 85%). Thereafter, crude 2-chlorophenyl indene was purified by high vacuum distillation. (Vaportemperature: 165-175° C., Vacuum: 0.7-0.8 mbar). After high vacuumdistillation: Weight=10 g (HPLC=96.6%), Yield: 73.7%

Above synthesized compound, 2-chloro phenylindene (5 g, 22.05 mmol),bis-pinacolato diboron (6.44 g, 25.36 mmol), triethyl amine (5.56 g, 55mmol), Ni(COD)₂ (217 mg), triphenyl phosphine (415 mg) and Methanol (50ml) was charged in to 100 ml RB flask. Resulted solution was heated toreflux (55° C.-57° C.) for an overnight. Then reaction was cooled to 10°C. and added dilute HCl (40 ml). Then added Dichloromethane (50 ml,Ethyl acetate also can be used), separated layers, organic layer washedwith saturated sodium chloride solution. Solvents removed by Rotaevaporator. Wt. of crude building block X (8.0 g).

The process of example 4 is illustrated by the below Scheme 4:

In Scheme 4, a compound of formula (12X), wherein R⁹, R¹⁰, R¹¹ and R¹²all stand for H and wherein X¹ stands for Br and wherein X² stands forCl is reacted with a compound of formula 5, wherein R¹, R², R³, R⁴, R⁵,R⁶, R¹³ and R¹⁴ all stand for H in a solvent (toluene) in the presenceof a Pd catalyst (Pd(PPh₃)₄) and a base (TBAOH=Tetra butyl ammoniumhydroxide) to form the corresponding compound of formula (13) andreacting the compound of formula (13) with the compound of formula 14Xin a solvent, in the presence of Ni(COD)₂, triphenylphosphine and a baseto form the corresponding compound of formula (1X) (also referred toherein as building block X).

Example 5. Preparation of Bis(2-Indenyl) Biphenyl from Building Block X

Building block X (8.0 g), building block Y, tetra butyl ammoniumhydroxide (25.13 ml, 1M solution in methanol), tetrakispalladiumtriphenyl phosphine (200 mg) and toluene (120 ml) were addedinto a roundbottom flask and the resulting solution was heated to reflux(78° C.-80° C.) and the product immediately started to precipitate outand heating was continued for 3 hours. Then TLC was used and it showedcompletion of the reaction. Then the reaction was cooled down to 10° C.,dilute HCl (50 ml) was added, stirred for 10 minutes and the solutionwas filtered off, the residue was washed with water and methanol anddried in an oven to afford 3 g of product. (2,2′-bi(2-indenyl)biphenyl).

The process of example 5 is illustrated by the below Scheme 5:

In Scheme 5, the compound of formula (1), wherein R¹, R², R³, R⁴, R⁵,R⁶, R⁹, R¹⁰, R¹¹ and R¹² all stand for H and wherein R⁷ and R⁸ togetherwith the oxygen atoms to which they are bound for a pinacolyl ring(building block X) is reacted with the compound of formula (2), whereinR¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² all stand for H and whereinX⁵ stands for Br (building block Y) in a solvent in the presence of a Pdcatalyst (Pd(PPh₃)₄) and a base.

2,2′-bis(2-indenyl)biphenyl]zirconiumdichloride

2,2′-bis(2-indenyl) biphenyl]zirconiumdichloride (the compound offormula (15), wherein R¹, R² R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ andR¹² all stand for H, wherein M stands for Zr and wherein Q stands for Cland wherein k stands for 2 can be prepared from2,2′-bis(2-indenyl)biphenyl (the compound of formula (3), wherein (R¹,R² R¹, R², R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² all stand for H) asdescribed in EP1059300A1, example VIII.4, [0106] and [107]:

“A 100 cc Schlenk charged with a stirring bar and2,2′-bis(2-indenyl)biphenyl (3.84 g, 10.0 mmol) was brought under anatmosphere of dry. Dry ether (40 mL) was added. The resulting suspensionwas cooled to 0° C. by ice-bath, and a solution of n-butyllithium (1.6 Min hexanes, 12.5 mL, 20.0 mmol) was added. The mixture was allowed towarm to room temperature. slowly. The crystals slowly dissolved, while afine suspension formed. Stirring at room temperature was continued for 4hour.

Meanwhile, a suspension of zirconium tetrachloride (2.34 g, 10 mmol) indry ether (40 mL) was prepared. The suspensions (of dianion in ether andof zirconium tetrachloride in ether) were cooled in an acetone/dry icebath, and mixed via a bended connection tube. The temperature wasallowed to rise to room temperature. After stirring for two days, thesuspension was filtered (under nitrogen atmosphere), and the residuewashed with dry ether three times (the last washing was colourless). Theresidue was dissolved partly in boiling toluene (260 mL), and thesuspension filtered hot under an atmosphere of dry nitrogen The clearyellow filtrate was cooled slowly to ambient temperature, giving yellowcrystals of pure product (3.30 g, 6.08 mmol, 60.6%). The filtrate wasused to extract the residue once more (boiling), and cooling to −20 DEGC. afforded another crop (0.65 g, 1.2 mmol, 12%).”

2,2′-bis(2-indenyl) biphenyl zirconiumdichloride can then be placed on asupport as described in EP1059300A1, paragraphs [0109] and [0110]:

“Supported 2,2′-bis(2-indenyl)biphenyl zirconiumdichloride

Silica (Grace Davison 2101) was heated at 200° C. under a stream ofnitrogen for 6 hours. To 7.3 g of this silica was added 70 ml oftoluene. The slurry was stirred and 49.4 ml of a 10 wt-% ofmethylalumoxane (diluted from a 30 wt % solution in toluene obtainedfrom Albemarle) was added slowly. The resulting slurry was stirred for16 hours at room temperature (20° C.), after which the solvent wasremoved by evaporation at 30° C.

To a slurry of 2.1 g of the obtained solid in 30 ml of toluene was addeda solution of 24 mg of [2,2′-bis(2-indenyl)biphenyl]-zirconiumdichloridein 20 mL of toluene, and the resulting slurry was stirred overnight. Theslurry was then decanted and dried by evaporation at 35° C.”

An improved way of preparing the supported 2,2′-bis(2-indenyl)biphenylzirconiumdichloride from diphenyl(2-indenyl)₂ZrCl₂ is described in WO2013/097936A1, example 9:

Example 9. Large Scale Preparation of the Catalyst Composition of theInvention

At room temperature, 0.595 kg of diphenyl(2-indenyl)₂ZrCl₂ was added to36.968 kg of a 30% methylaluminoxane solution (Al content 13.58 wt %)and stirred for 30 minutes to form activated metallocene. About 172 kgof dry toluene was added to 43 kg of silica 955 to form a silica slurry.At about 30° C., the activated metallocene was added to the silicaslurry under agitation. After the activated metallocene was added, thetemperature was increased to 50° C. After 2 hours at 50° C., all ofmodifier F (wherein modifier F was prepared by, at room temperature,slowly adding 0.114 kg of neat triisobutylaluminum to a solution of0.059 of cyclohexylamine in 9.7 kg of dry toluene) was added. Afteraddition the mixture was kept at 50° C. for 1 hour. The reactiontemperature was then reduced to 30° C. The toluene was removed byfiltration and the obtained catalysts composition was dried by raisingthe temperature to 55° C. and using a flow of warm nitrogen. The Al/Zrratio used in this experiment was approximately 150.”

The supported 2,2′-bis(2-indenyl)biphenyl zirconiumdichloride can thenbe used in a polymerization, for example as described in WO2013/097936A1or for example as described in EP1059300A1, examples X-IX:

“400 ml of pentamethyl heptane (abbreviation: PMH), ethylene and,eventually, 25 ml 1-octene were supplied to a 1.3-liter reactor, withheating to polymerisation temperature (Tp); the pressure was 2 MPa.Next, 0.78 ml (1.6 M solution in toluene) of methylaluminoxane (Witco)and the catalyst solution or slurry (0.125 ml of a 0.001 m solution intoluene) were premixed at room temperature for 1 minute and thensupplied to the reactor. The catalyst supply vessel was rinsed out with100 ml of pentamethylheptane (PMH). The pressure in the reactor was keptconstant by supplying ethene. By cooling the reactor the temperaturedeviation from the setting was limited to a maximum of 5° C. After 10minutes the polymerisation was stopped and the polymer was worked up bydraining the solution and boiling it down under vacuum at 50° C.”.

The invention claimed is:
 1. A process comprising reacting a compound offormula (1)

wherein R¹, R², R³, R⁴, R⁵ and R⁶ each independently stand for H or ahydrocarbon radical having 1-20 C-atoms, and wherein R⁷ and R⁸ eachindependently stand for H, or an alkyl or aryl or wherein R⁷ and R⁸optionally form a ring together with the oxygen atoms to which they arebound, with a compound of formula (2)

wherein R^(1a), R^(2a), R^(3a), R^(4a), R^(5a), and R^(6a) eachindependently stand for H or a hydrocarbon radical having 1-20 C-atoms,and wherein X⁵ stands for a halogen in a solvent in the presence of a Pdcatalyst and a base, to form the corresponding compound of formula (3)

wherein, in formula (3), R¹, R², R³, R⁴, R⁵, R^(1a), R^(2a), R^(3a),R^(4a), R^(5a), and R^(6a) are as defined in formula (1) and formula(2), respectively, wherein the solvent is an aromatic solvent, an ethersolvent, an alcohol solvent, water, or a combination comprising at leastone of the foregoing, wherein the Pd catalyst is a Pd(0) catalyst, andwherein the base is a quaternary ammonium salt, a tertiary amine, or analkali or alkaline earth metal salt of acetate, alkoxide, carbonate,halide, hydroxide, or phosphate.
 2. The process according to claim 1,wherein R¹, R², R³, R⁴, R⁵, R⁶, R^(1a), R^(2a), R^(3a), R^(4a), R^(5a),R^(6a) are hydrogen.
 3. The process according to claim 1, wherein R⁷ andR⁸ are hydrogen.
 4. The process according to claim 1, wherein R⁷ and R⁸form a pinacolyl ring together with the oxygen atoms to which they arebound.
 5. The process according to claim 1, wherein X⁵ is Cl or Br. 6.The process according to claim 1, wherein the Pd catalyst istetrakis(triphenylphosphine) palladium (0), tris(dibenzylideneacetone)dipalladium(0), bis(tricyclohexylphosphine) palladium(0),bis(tri-t-butylphosphine) palladium(0),bis[1.2-bis(diphenylphosphino)ethane] palladium(0), or palladium oncarbon.
 7. The process according to claim 1, wherein the Pd catalyst isPd(PPh₃)₄.
 8. The process according to claim 1, wherein the solvent ismethanol, ethanol, benzene, toluene, xylene, tetrahydrofuran, dioxane,dimethoxyethane, water, or a combination comprising at least one of theforegoing.
 9. The process according to claim 1, wherein the solvent istoluene.
 10. The process according to claim 1, wherein the base istetrabutylammonium hydroxide, tetra n-butylammonium acetate,triethylamine, sodium carbonate, sodium acetate, sodium tert-butoxide,potassium carbonate, potassium iodide, sodium iodide, potassium acetate,cesium carbonate, cesium fluoride, lithium hydroxide, sodium hydroxide,sodium ethoxide, potassium fluoride, or potassium phosphate.